The process e+e-→Ds∗+Ds0∗(2317)-+c.c. is observed for the first time with the data sample of 567 pb-1 collected with the BESIII detector operating at the BEPCII collider at a center-of-mass energy s=4.6 GeV. The statistical significance of the Ds0∗(2317)± signal is 5.8σ and the mass is measured to be (2318.3±1.2±1.2) MeV/c2. The absolute branching fraction B(Ds0∗(2317)±→π0Ds±) is measured as 1.00-0.14+0.00(stat)-0.14+0.00(syst) for the first time. The uncertainties are statistical and systematic, respectively.